Corroxion Protective Methacrylate Adhesives for Galvanized Steel and Other Metals

ABSTRACT

Compositions for bonding galvanized surfaces are disclosed. The compositions include either (i) a first part that includes at least one (meth)acrylate component in combination with a free radical inhibitor component and a phosphate ester component and a second part that includes at least one accelerator component or (ii) a first part that includes at least one (methyl)acrylate component in combination with an accelerator and a phosphate ester component and a second part that includes a carrier component and a free radical initiator component. Methods for preparing and methods for using these compositions also are disclosed, as are processes for inhibiting corrosion on galvanized surfaces.

FIELD OF THE INVENTION

The present invention relates generally to compositions for bondinggalvanized surfaces and articles of manufacture that contain suchcompositions. The present invention also relates to methods forpreparing the aforementioned compositions and methods of using suchcompositions. Moreover, the present invention relates to processes forinhibiting corrosion on a galvanized surface.

BACKGROUND OF RELATED TECHNOLOGY

Metal surfaces that are coated with zinc-containing compositions or zincalloy-containing compositions (e.g., Galfan® and Galvaluene®) oftenexhibit better corrosion resistance than surfaces that are not coatedwith such compositions. Accordingly, galvanized (i.e., zinc-coated orzinc alloy-coated) surfaces are routinely utilized in a variety ofindustries, including the construction, vehicle, and applianceindustries.

Even galvanized surfaces, however, are susceptible to corrosion overprolonged periods of time. Such corrosion, of course, comprises theintegrity of products assembled with those products (particularly atbond lines), often rendering such products poorly suited or unsuitablefor commercial use.

Moreover, it is well-known that it is difficult to bond galvanizedsurfaces together by means of conventional adhesives. Indeed,conventional adhesive compositions demonstrate poor adhesion togalvanized surfaces at room temperature. More significantly, whenexposed to conditions of heat and humidity, conventional adhesivecompositions exhibit minimal, if any, tensile strength.

Consequently, galvanized surfaces have traditionally been joinedtogether by welding or mechanical fixing means (e.g., screws, rivets,and lock-forming means). Joining surfaces by welding or mechanicalfixing means, however, is labor-intensive and expensive, and does notprovide the advantages attendant use of adhesive compositions (e.g.,weight-saving advantages, ease of preparation, and cost-effectiveness).

Thus, it would be desirable to provide compositions that (i) demonstrateimproved bond strength on galvanized surfaces under various conditions,particularly under conditions of heat and humidity, and (ii) minimizeand/or prevent corrosion on galvanized surfaces.

SUMMARY OF THE INVENTION

In one aspect of the invention, there is provided a curable compositionfor bonding galvanized surfaces including: (a) a first part including:(i) at least one curable (meth)acrylate component; (ii) a free-radicalinitiator component; and (iii) a phosphate ester component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 1000 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including anaccelerator component, wherein at least the first part or the secondpart also includes a corrosion inhibitor.

In another aspect of the invention, there is provided a method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, at least one free-radical initiator component, and aphosphate ester component, wherein the phosphate ester component ispresent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 1000 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; (b)forming a second part including at least one accelerator component; and(c) combining parts (a) and (b) under conditions sufficient toeffectuate cure, wherein a corrosion inhibitor is admixed with at leastthe first part or the second part.

In another aspect of the invention, there is provided a method for usinga curable composition to bond together two substrates, including thesteps of. (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withcomposition-applied first substrate surface to form an assembly; and (c)maintaining the abutting relationship for a time sufficient to allow thecomposition to cure, wherein at least one of the abutting substratesurfaces is galvanized and wherein the composition includes: (a) a firstpart including: (i) at least one curable (meth)acrylate component; (ii)a free-radical initiator component; and (iii) a phosphate estercomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 1000 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; and(b) a second part including an accelerator component, wherein at leastthe first part or the second part also includes a corrosion inhibitor.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) a free-radical initiator component; and (iii) aphosphate ester component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 1000 psi whenmeasured after humidity aging at 85% relative humidity and 85° C. for250 hours; and (b) a second part including an accelerator component, and2.) subjecting the composition-applied substrate surface to conditionssufficient to allow the composition to cure, wherein at least the firstpart or the second part also includes a corrosion inhibitor.

In another aspect of the invention, there is provided a compositionincluding the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) a free-radicalinitiator component; and (iii) a phosphate ester component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 1000 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including anaccelerator, wherein at least the first part or the second part alsoincludes a corrosion inhibitor

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition for bonding galvanized surfaces, wherein atleast one of the substrate surfaces is galvanized and wherein thecomposition includes: (a) a first part including: (i) at least onecurable (meth)acrylate component; (ii) a free-radical initiatorcomponent; and (iii) a phosphate ester component in an amount sufficientto achieve a tensile strength on a galvanized surface of at least about1000 psi when measured after humidity aging at 85% relative humidity and85° C. for 250 hours; and (b) a second part including an acceleratorcomponent, wherein at least the first part or the second part alsoincludes a corrosion inhibitor.

In another aspect of the invention, there is provided a curablecomposition for bonding galvanized surfaces including: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) anaccelerator; and (iii) a phosphate ester component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 1000 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including: (i)a carrier component and (ii) a free radical initiator component, whereinat least the first part or the second part also includes a corrosioninhibitor.

In another aspect of the invention, there is provided a method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, an accelerator, and a phosphate ester component, wherein thephosphate ester component is present in an amount sufficient to achievea tensile strength on a galvanized surface of at least about 1000 psiwhen measured after humidity aging at 85% relative humidity and 85° C.for 250 hours;

(b) forming a second part by admixing at least one carrier component andat least one free radical initiator component; and (c) combining parts.(a) and (b) under conditions sufficient to effectuate cure, wherein acorrosion inhibitor is admixed with at least the first part or thesecond part.

In another aspect of the invention, there is provided a method for usinga curable composition to bond together two substrates, including thesteps of: (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withcomposition-applied first substrate surface to form an assembly; and (c)maintaining the abutting relationship for a time sufficient to allow thecomposition to cure, wherein at least one of the abutting substratesurfaces is galvanized and wherein the composition includes: (a) a firstpart including: (i) at least one curable (meth)acrylate component; (ii)an accelerator; and (iii) a phosphate ester component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 1000 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including: (i)a carrier component and (ii) a free radical initiator component, whereinat least the first part or the second part also includes a corrosioninhibitor.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of: 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) an accelerator; and (iii) a phosphate ester component inan amount sufficient to achieve a tensile strength on a galvanizedsurface of at least about 1000 psi when measured after humidity aging at85% relative humidity and 85° C. for 250 hours; and (b) a second partincluding: (i) a carrier component and (ii) a free radical initiatorcomponent, and 2.) subjecting the composition-applied substrate surfaceto conditions sufficient to allow the composition to cure, wherein atleast the first part or the second part also includes a corrosioninhibitor.

In another aspect of the invention, there is provided a compositionincluding the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) an accelerator; and(iii) a phosphate ester component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 1000 psi whenmeasured after humidity aging at 85% relative humidity and 85° C. for250 hours; and (b) a second part including: (i) a carrier component and(ii) a free radical initiator component, wherein at least the first partor the second part also includes a corrosion inhibitor.

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition for bonding galvanized surfaces, wherein atleast one of the substrate surfaces is galvanized and wherein thecomposition includes: (a) a first part including: (i) at least onecurable (meth)acrylate component; (ii) an accelerator; and (iii) aphosphate ester component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 1000 psi whenmeasured after humidity aging at 85% relative humidity and 85° C. for250 hours; and (b) a second part including: (i) a carrier component and(ii) a free radical initiator component, wherein at least the first partor the second part also includes a corrosion inhibitor.

In another aspect of the invention, there is provided a curablecomposition for bonding galvanized surfaces including: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) afree-radical initiator component; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 2500 psi atroom temperature; and (b) a second part including an acceleratorcomponent.

In another aspect of the invention, there is provided a method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, at least one free-radical initiator component, a phosphateester component, and an organic acid component in an amount sufficientto achieve a tensile strength on a galvanized surface of at least about2500 psi at room temperature; (b) forming a second part including atleast one accelerator component; and (c) combining parts (a) and (b)under conditions sufficient to effectuate cure.

In another aspect of the invention, there is provided a method for usinga curable composition to bond together two substrates, including thesteps of: (a) applying the composition to a first substrate surface;(b.) mating the surface of a second substrate in abutting relationshipwith composition-applied first substrate surface to form an assembly;and (c) maintaining the abutting relationship for a time sufficient toallow the composition to cure, wherein at least one of the abuttingsurfaces is galvanized and wherein the composition includes: (a) a firstpart including: (i) at least one curable (meth)acrylate component; (ii)a free-radical initiator component; (iii) a phosphate ester component;and (iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 2500 psi atroom temperature; and (b) a second part including an acceleratorcomponent.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of: 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) a free-radical initiator component; (iii) a phosphateester component; and (iv) an organic acid component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 2500 psi at room temperature; and (b) a second partincluding an accelerator component, and 2.) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.

In another aspect of the invention, there is provided a compositionincluding the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) a free-radicalinitiator component; (iii) a phosphate ester component; and (iv) anorganic acid component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 2500 psi at roomtemperature; and (b) a second part including an accelerator.

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition for bonding galvanized surfaces, wherein atleast one of the substrate surfaces is galvanized and wherein thecomposition includes: (a) a first part including: (i) at least onecurable (meth)acrylate component; (ii) a free-radical initiatorcomponent; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 2500 psi at room temperature; and(b) a second part including an accelerator component.

In another aspect of the invention, there is provided a curablecomposition for bonding galvanized surfaces including: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) anaccelerator; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 2500 psi at room temperature; and(b) a second part including: (i) a carrier component and (ii) a freeradical initiator component.

In another aspect of the invention, there is provided a, method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, a free radical initiator component, a phosphate estercomponent, and an organic acid component in an amount sufficient toachieve a tensile strength on a galvanized surface of at least about2500 psi at room temperature: (b) forming a second part including atleast one accelerator component: and (c) combining parts (a) and (b)under conditions sufficient to effectuate cure.

In another aspect of the invention, there is provided a method for usinga curable composition for bonding galvanized surfaces, including thesteps of: (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withcomposition-applied first substrate surface to form an assembly; and (c)maintaining the abutting relationship for a time sufficient to allow thecomposition to cure, wherein at least one of the abutting surfaces isgalvanized, and wherein the composition includes: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) anaccelerator; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 2500 psi at room temperature; and(b) a second part including: (i) a carrier component and (ii) a freeradical initiator component.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of: 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) an accelerator; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 2500 psi atroom temperature, and (b) a second part including: (i) a carriercomponent and (ii) a flee radical component, and 2.) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.

In another aspect of the invention, there is provided a compositionincluding the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) an accelerator; (iii) aphosphate ester component; and (iv) an organic acid component in anamount sufficient to achieve a tensile strength on a galvanized surfaceof at least about 2500 psi at room temperature; and (b) a second partincluding: (i) a carrier component and (ii) a free radical initiatorcomponent.

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition, wherein at least one of the substratesurfaces is galvanized and wherein the composition includes: (a) a firstpart including: (i) at least one curable (meth)acrylate component; (ii)an accelerator; (iii) a phosphate ester component; and (iv) an organicacid component in an amount sufficient to achieve a tensile strength ona galvanized surface of at least about 2500 psi at room temperature; and(b) a second part including: (i) a carrier component and (ii) a freeradical initiator component.

In another aspect of the invention, there is provided a curablecomposition for bonding galvanized surfaces including: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) afree-radical initiator component; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 800 psi whenmeasured after humidity aging at 85% relative humidity and 85° C. for250 hours; and (b) a second part including an accelerator component.

In another aspect of the invention, there is provided a method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, an accelerator, a phosphate ester component, and an organicacid component in an amount sufficient to achieve a tensile strength ona galvanized surface of at least about 800 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; (b)forming a second part including at least one accelerator component; and(c) combining parts (a) and (b) under conditions sufficient toeffectuate cure.

In another aspect of the invention, there is provided a method for usinga curable composition to bond together two substrates, including thesteps of: (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withcomposition-applied first substrate surface to form an assembly; and (e)maintaining the abutting relationship for a time sufficient to allow thecomposition to cure, wherein at least one of the abutting surfaces isgalvanized and wherein the composition includes: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) afree-radical initiator component; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least 800 psi whenmeasured after humidity aging at 85% relative humidity and 85° C. for250 hours; and (b) a second part including an accelerator component.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of: 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) a free radical initiator component; (iii) a phosphateester component; and (iv) an organic acid component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 800 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including anaccelerator component; and 2.) subjecting the composition-appliedsubstrate surface to conditions sufficient to allow the composition tocure.

In another aspect of the invention, there is provided a compositioncomprising the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) a free radicalinitiator component; (iii) a phosphate ester component; and (iv) anorganic acid component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 800 psi when measuredafter humidity aging at 85% relative humidity and 85° C. for 250 hours;and (b) a second part including an accelerator component.

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition for bonding galvanized surfaces, wherein atleast one of the substrate surfaces is galvanized and wherein thecomposition includes: (a) a first part including: (i) at least onecurable (meth)acrylate component; (ii) a free-radical initiatorcomponent; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 800 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; and(b) a second part including an accelerator component.

In another aspect of the invention, there is provided a curablecomposition for bonding galvanized surfaces including: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) anaccelerator; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on aGalvanized surface of at least about 800 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; and(5) a second part including: (i) a carrier component and (ii) a freeradical initiator component.

In another aspect of the invention, there is provided a method forpreparing a composition for bonding galvanized surfaces including: (a)forming a first part by admixing at least one curable (meth)acrylatecomponent, an accelerator. a phosphate ester component, and an organicacid component in an amount sufficient to achieve a tensile strength ona galvanized surface of at least about 800 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; (b)forming a second part including: (i) a carrier component and (ii) a freeradical initiator component; and (c) combining parts (a) and (b) underconditions sufficient to effectuate cure.

In another aspect of the invention, there is provided a method for usinga curable composition to bond together two substrates, including thesteps of: (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withcomposition-applied first substrate surface to form an assembly; and (c)maintaining the abutting relationship for a time sufficient to allow thecomposition to cure, wherein at least one of the abutting surfaces isgalvanized and wherein the composition includes: (a) a first partincluding: (i) at least one curable (meth)acrylate component; (ii) anaccelerator; (iii) a phosphate ester component; and (iv) an organic acidcomponent in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 800 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours; and(b) a second part including: (i) a carrier component and (ii) a freeradical initiator component.

In another aspect of the invention, there is provided a process forinhibiting corrosion on a galvanized surface including the steps of: 1.)applying to a galvanized substrate surface a composition including: (a)a first part including: (i) at least one curable (meth)acrylatecomponent; (ii) an accelerator; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 800 psi whenmeasured after humidity aging at 85% relative hunidity and 85° C. for250 hours; and (b) a second part including: (i) a carrier component and(ii) a free radical initiator component; and 2.) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.

In another aspect of the invention, there is provided a compositionincluding the reaction product of: (a) a first part including: (i) atleast one curable (meth)acrylate component; (ii) an accelerator; (iii) aphosphate ester component; and (iv) an organic acid component in anamount sufficient to achieve a tensile strength on a galvanized surfaceof at least about 800 psi when measured after humidity aging at 85%relative humidity and 85° C. for 750 hours; and (b) a second partincluding: (i) a carrier component and (ii) a free radical initiatorcomponent.

In another aspect of the invention, there is provided an article ofmanufacture including at least two substrate surfaces bonded togetherwith a curable composition for bonding galvanized surfaces, wherein atleast one of the substrate surfaces is galvanized and wherein thecomposition includes: (a) a first part including: (i) at least onecurable (meth)acrylate component; (ii) an accelerator; (iii) a phosphateester component; and (iv) an organic acid component in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 800 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours; and (b) a second part including: (i)a carrier component and (ii) a free radical initiator component.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to compositions for bonding galvanizedsurfaces, to methods of preparing such compositions, and to methods ofusing such compositions to bond together substrates, particularlygalvanized substrate surfaces. Moreover, the present invention isdirected to processes that utilize the present inventive compositions toinhibit corrosion on galvanized surfaces.

The present inventive compositions include two parts, i.e., a first partand a second part. In particular, they are formulated to include either(i) a first part that includes at least one (meth)acrylate component incombination with a free radical inhibitor component and a phosphateester component and a second part that includes at least one acceleratorcomponent or (ii) a first part that includes at least one (meth)acrylatecomponent in combination with an accelerator and a phosphate estercomponent and a second part that includes a carrier component and a freeradical initiator component Moreover, it is desirable to include acorrosion inhibitor, as well as an organic acid component, in thepresent inventive compositions.

Useful (meth)acrylate components can be chosen from a wide variety ofmaterials represented by the following formula:

where G may be hydrogen, halogen or alkyl of 1 to about 4 carbon atoms,and R¹ may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl,alkaryl, aralkyl or aryl groups of 1 to about 16 carbon atoms, any ofwhich may be optionally substituted or interrupted as the case may bewith silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester,carboxylic acid, urea, urethane, carbamate, amine, amide, sulfur,sulfonate, sulfone, and the like.

Additionally, useful (meth)acrylate components can be chosen from thealkylene glycol diacrylates having the general formula:

wherein R₄ is selected from the group consisting of hydrogen, halogen,and lower alkyl of 1-4 carbon atoms; R₅ is selected from the groupconsisting of hydrogen, —OH,

R₆ is a radical selected from the group consisting of hydrogen, loweralkyl of 1-4 carbon atoms, hydroxyalkyl of 1-4 carbon atoms, and m is aninteger equal to at least 1, desirably 1-8 and more desirably from 1 to4; n is an integer equal to at least 1, desirably, 1 to 20; and p is 0or 1.

Typical of these monomers are mono-, di-, tri- tetra- and polyethyleneglycol dimethacrylate and the corresponding diacrylates;dipentamethylene glycol) dimethacrylate; tetraethylene glycoldi(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate;butylene glycol dimethacrylate; neopentyl glycol diacrylate; andtrimethylopropane triacrylate.

Particularly useful polymerizable crosslinkable components that can beused as the (meth)acrylate component are ethoxylated trimethylolpropanetriacrylate, trimethylol propane trimethacrylate, dipentaaerythritolmonohydroxypentacrylate, pentaerythritol triacrylate, ethoxylatedtrimethylolpropane triacrylate, 1,6-hexanedioldiacrylate, neopertylglycoldiacrylate, pentaerythritol tetraacrylate, 1,2-butyleneglycoldiacrylate, trimethylopropane ethoxylate tri(meth)acrylate,glyceryl propoxylate tri(meth)acrylate, trimethylolpropanetri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate,tri(propylene glycol) di(meth)acrylate, neopentylglycol propoxylatedi(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethyleneglycoldi(meth)acrylate, triethyleneglycol di(meth)acrylate, butylene glycoldi(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate andcombinations thereof. Moreover, MHORMER BM-905 (hydroxy ethylmethacrylate monomer (HEMA)) can be incorporated in the presentinventive compositions as the (meth)acrylate component.

Various useful urethane-acrylate monomers, such as those described inU.S. Pat. No. 3,925,988 to Gorman, and U.S. Pat. No. 4,309,526 toBaccei, each of which are incorporated herein by reference, also may beused as the (meth)acrylate component. The monomers disclosed in the '526patent may be viewed as one-component polymerizable block copolymers(prepolymers) having rigid and flexible segments. This is achieved bythe chemical linking of precursor “prepolymers” which are subsequently“capped” with (meth)acrylate functionality.

Moreover, acrylates derived from bisphenol-A, such as bisphenol-Adimethacrylate, hydrogenated bisphenol-A dimethacrylate, and ethoxylatedbisphenol-A dimethacrylate also may be used as the (meth)acrylatecomponent.

Furthermore, while di- and other polyacrylate esters have been foundparticularly desirable, monofunctional acrylate esters (esterscontaining one acrylate group) also may be used as the (meth)acrylatecomponent. When dealing with monofunctional acrylate esters, it isdesirable to use an ester which has a relatively polar alcoholic moiety.Such materials are less volatile than low molecular weight alkyl estersand, more importantly, the polar group tends to provide intermolecularattraction during and after cure, thus producing more desirable cureproperties, as well as a more durable sealant or adhesive. Particularlydesirable are the polar groups selected from labile hydrogen,heterocyclic ring, hydroxy, amino, cyano, and halogen polar groups.Useful examples of compounds within this category include cyclohexylmethacrylate, tetrahydrofurfuryl methaerylate, hydroxyethyl acrylate,hydroxypropyl methacrylate, t-butylaminoethyl methacrylate,cyanoethylacrylate, and chloroethyl methacrylate. The materials areoften incorporated as reactive diluents which are capable ofcopolymerizing with the various other polymerizable materials.

Other unsaturated reactive diluents, such as styrene and acrylonitrile,also can be used. When used, the concentration of such diluents shouldbe less than about 60 percent by weight, and preferably about 10 toabout 40 percent by weight of the total composition. As used herein, thephrase total composition refers to a composition having a first part anda second part.

A particularly useful curable (meth)acrylate component for use in thepresent inventive compositions is methyl methacrylate. The usefulamounts of (meth)acrylate component typically range from about 40% byweight to about 70% by weight of the total composition.

A number of well-known initiators of free radical polymerization may beincorporated in the present invention as the free-radical initiatorcomponent. Peroxides and peresters are particularly useful For example,suitable initiators of free radical polymerization include, withoutlimitation, cumene hydroperoxide (CHP), paramenthane hydroperoxide,tertiary butyl hydroperoxide (TBH), tertiary butyl perbenzoate (TBPB),and benzoyl peroxide (BPO). The useful amounts of free-radical initiatorcomponent typically range from about 0.5% by weight to about 3% byweight of the total composition.

The compositions of the present invention can include any suitablephosphate ester. Suitable phosphate esters for use in the presentinvention include those represented by the formula:

wherein R¹ is H or CH₃, and R² is H, and wherein R² can additionallyinclude:

wherein R¹ is H or CH₃. A particularly useful phosphate ester for use inthe present invention is HEMA phosphate ester, which is sold under thetradename T-MULZ 1228.

Desirably, the phosphate ester component is present in the inventivecompositions in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 1000 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 250 hours.Moreover, the phosphate ester component is desirably present in theinventive compositions in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 2500 psi at roomtemperature. More particularly, the phosphate ester component is presentin an amount sufficient to achieve at least a 20% increase in tensilestrength on galvanized surfaces as compared to compositions notcontaining a phosphate ester component. The useful amounts of phosphateester component typically range from about 2% by weight to about 5% byweight of the total composition.

Various accelerator compounds, such as tertiary amines, imides,polyamines, cyclicamines, and arylamines can be included in thecompositions of the present invention to further increase cure speedsand completion of cure. See, e.g., U.S. Pat. No. 3,041,322(tertiaryamines), U.S. Pat. No. 3,046,282 (imides), U.S. Pat. No.3,203,941 (polyamines), U.S. Pat. No. 3218,305 (cyclic and arylamines),and U.S. Pat. No. 3,591,438, all to Kriebel, the disclosures of whichare all incorporated herein by reference.

Other useful accelerators for the present invention include compoundshaving the following formula:

wherein R¹ is selected from alkyl from 2 to 6 carbon atoms, cycloalkyl,aryl, alkenyl, and cycloalkenyl and R² is selected from hydrogen, alkyl,cycloalkyl, alkenyl and cycloalkenyl, aryl, alkoxy, aryloxy, carbonyl,amino, and the following groups:

wherein R¹⁰ is selected from alkyl groups containing one to about 10carbon atoms, alkenyl groups containing two to about 10 carbon atoms,and aryl groups containing up to about 10 carbon atoms. Examples ofuseful accelerator compounds include 1-acetyl-2-phenyl hydrazine,1-acetyl-2(p-tolyl) para-toluene sulfonyl hydrazide, 1-formyl-2-phenylhydrazine and combinations thereof.

Particularly useful accelerators that can be incorporated in the presentinventive compositions include pyridine derivatives having the formula:

One particularly useful pyridine derivative is sold under the tradenameREILLCAT ASY-2.

Suitable accelerators for the free-radical initiator component includephenyl dihydro pyridine (PDHP), transition metals, such as copper,cobalt, magnesium, vanadium, manganese, iron, and salts and complexesthereof saccharin, and alkylated aromatic amines, such as dimethylp-toluidine (DMPT), and derivatives of alkylated aromatic amines. Metalsalt solutions such as copper salt solutions are particularly useful.More particularly, acetyl acetone metal complexes such as 2,4-pentanedione/copper complexes and naphthenate/copper complexes are useful. Forexample, the commercially available IMN2231 (copper naphthenate inmethyl methacrylate) can be included in the present inventivecompositions.

The useful amounts of accelerator typically range from about 0.1% byweight to about 6% by weight of the total composition. Desirably, PDHPis present in an amount from about 1% by weight to about 3% by weight ofthe total composition.

With respect to the present inventive compositions that include a firstpart that includes at least one curable (meth)acrylate component incombination with a free-radical initiator component and a phosphateester component and a second part that includes an acceleratorcomponent, the free radical initiator component is desirably TBPB orCHP, and a catalyst (e.g., an amine or transition metal reducing agent)is desirably also included in the second part. When a peroxide andcatalyst are included in such compositions, the ratio of peroxide tocatalyst can be any suitable ratio. Suitable ratios of peroxide tocatalyst include, for example, 1:1 to 10:1.

With respect to the present inventive compositions that include a firstpart that includes at least one curable (meth)acrylate component incombination with an accelerator and a phosphate ester component and asecond part that includes a free-radical initiator, the free-radicalinitiator component is desirably BPO, and a catalyst (e.g., DMPT) isdesirably also included in the first part. When a peroxide and catalystare included in such compositions, the ratio of peroxide to catalyst canbe any suitable ratio. Suitable ratios of peroxide to catalyst include,for example, 1:1 to 10:1. Desirably, the ratio of peroxide to catalystis 10:1.

Any suitable carrier component can be used in the present inventivecompositions. The primary purpose of the carrier component is to serveas a vehicle for the accelerator, catalyst or free-radical initiatorcomponent in the second part. Suitable carrier components include, forexample, reactive resins and non-reactive resins. Desirably, thereactive resin is a (meth)acrylate resin.

Any suitable corrosion inhibitor can be used in the present invention.Suitable non-limiting commercially available corrosion inhibitorsinclude, for example, metal phospho-silicates and alkali metalphospho-silicates. Other useful inhibitors include, for example, phenolssuch as hydroquinione and quinones. Suitable inhibitors also include,for example, Halox® SZP-391 (strontium zinc phosphosilicate), Halox®CZ-170 (phosphate), Halox® Z-Plex 111 (phosphosilicate), Saci® 760,Cotrol® 18-8 (dialkylamino alkanoate, metal salt), Cotrol® 316-FG (freeflowing powder, based on calcium silico phosphate), Cotrol® BMB (bariummetaborate), Cotrol® AMB (ammonium benzoate), VCI (Vapor Phase CorrosionInhibitor), Irgacor 252 LD Qbenzothiazole succinate),8-hydroxyquinoline, and combinations thereof. A particularly usefulinhibitor is Halox® CW-491 (calcium phosphosilicate).

The corrosion inhibitor can be present in the present inventivecompositions in an amount sufficient to achieve a tensile strength on agalvanized surface of at least about 400 psi when measured afterhumidity aging at 85% relative humidity and 85° C. for 500 hours. Theuseful amounts of corrosion inhibitor typically range from about 1% byweight to about 15% by weight of the total comnposition. Desirably, thecorrosion inhibitor is present in an amount from about 3% by weight toabout 10% by weight of the total composition.

Any suitable organic acid component can be used in the presentinvention. Suitable organic acids include, for example, carboxylicacids. Suitable carboxylic acids include, for example, methacrylic acid,maleic acid, acrylic acid, fumeric acid, and acid derivatives of acrylicand methacrylic acid, such as beta carboxy ethyl acrylic acid (BCEA),and other carboxylic acids and derivatives thereof that would be knownto one of ordinary skill in the art. A particularly useful organic acidthat can be incorporated in the present inventive compositions ismethacrylic acid.

Desirably, the organic acid component is incorporated in the presentinventive compositions in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 2500 psi at roomtemperature. Moreover, the organic acid component is desirablyincorporated in the present inventive compositions in an amountsufficient to achieve a tensile strength on a galvanized surface of atleast about 800 psi when measured after humidity aging at 85% relativehumidity and 85° C. for 250 hours.

The useful amounts of organic acid typically range from about 1% byweight to about 9% by weight of the total composition. Desirably, theorganic acid is present in an amount of at least about 2% by weight ofthe total composition and, more desirably, about 3% by weight to about5% by weight of the total composition.

Desirably, methacrylic acid is present in an amount of about 1% byweight to about 9% by weight of the total composition. More desirably,methacrylic acid is present in an amount of about 2% by weight of thetotal composition to about 4% by weight of the composition.

Any suitable toughening component can be used in the present invention.In particular, the toughening component of the present invention can bechosen from a wide variety of elastomeric materials that form discreteparticles or biphasic domains in a continuous resin matrix. For example,prereacted particles of polyacrylate, styrene/butadiene/styrene (SBS)copolymers, styrene/isoprene/styrene (SIS) copolymers, styrene/butadiene(SBR) copolymers, as well as other prereacted materials may be added inparticulate form to the resin composition. A partial listing of usefulprereacted elastomer rubbers includes prereacted elastomer particlesselected from the group consisting of acrylate-butadiene, butadiene,chloroprene, ethylene-propylene, ethylene-propylene-diene, isoprene,isobutylene, isobutylene-isoprene (butyl rubber), styrene-butadiene,styrene-isoprene, acrylonitrile-butadiene, acrylonitrile-chloroprene,vinylpyridine-butadiene, vinylpyridine-styrene-butadiene,carboxylic-styrene-butadiene, chloroisobutylene-isoprene (chlorobutylrubber), bromoisobutylene-isoprene (bromobutyl rubber), dialkysiloxane,poly(propylene oxide), polyesteruethanes, polyetherurethanes, andmixtures thereof. Moreover, reactive liquid polymers (RLP's) also can beincorporated as the toughening component. RLP's contain functionalgroups, usually on their terminal ends but occasionally as pendantgroups, and react with the resin in situ to form elastomeric domains.Examples of RLP's include, without limitation, carboxy-terminatedbutadiene nitrile (CTBN), amine-terminated butadiene nitrile (ATBN),hydroxy-terminated butadiene nitrite (HTBN), epoxy-terminated butadienenitrile (ETBN), mercapto-terminated butadiene nitril (MTPN), andphenoxy-terminated butadiene nitrite (PTBN).

Particularly useful agents that can be utilized as the tougheningcomponent include, for example, Blendex 338, nitrile rubber, andchlorosulfonated polyethylenes represented by the structure:

Particularly useful chlorosulfonated polyethylenes include, for example,Hypalon 20 and Hypalon 30.

The useful amounts of the toughening component typically range fromabout 5% by weight to about 60% by weight of the total composition.Desirably, the toughening component is present in an amount of about 10%by weight to about 50% by weight of the total composition.

Chelating agents also may be employed to control and prevent prematureperoxide decomposition and polymerization, as well as to remove traceamounts of metal contaminants. Examples of useful chelating agent arethe tetrasodium salt of ethylenediamine tetraacetic acid (EDTA) andbutylated hydroxy toluene (BHT). Useful amounts of a chelating agenttypically range from about 0.01% by weight to about 2% by weight of thetotal composition. Desirably, the chelating agent is present in anamount of from about 0.02% by weight to about 0.2% by weight of thetotal composition.

Any suitable antioxidant can be included in the present inventivecompositions Particularly useful antioxidants are phenolic antioxidants,such as Naugard BHT and hydroquinone. Useful amounts of antioxidantstypically range from about 10 ppm to about 3% by weight of the totalcomposition. Desirably, antioxidants are present in an amount of fromabout 0.5% by weight to about 1.5% by weight of the total composition.

Any suitable thixotrope can be included in the present inventivecompositions. Suitable thixotropic agents include, for example,Disparlon 6100, Disparlon 6200, organo clay, and polyamide powder.Useful amounts of thixotropes typically range from about 0% by weight toabout 10% by weight of the total composition. Desirably, a thixotrope ispresent in an amount from about 0.5% to about 3% by weight of the totalcomposition.

Any suitable blooming agent can be included in the present inventivecompositions. A suitable blooming agent is, for example, paraffin wax.Useful amounts of wax typically range from about 0.1% by weight to about3% by weight of the total composition. Preferably, wax is present in anamount from about 0.2% by weight to about 1.5% by weight of the totalcomposition.

Any suitable filler can be included in the present inventivecompositions. Suitable fillers include, for example, nephyline syenite,alkali metal carbonates, and silicas. Useful amounts of filler typicallyrange from about 0% to about 70% by weight of the total composition.Desirably, fillers are present in an amount from about 0% by weight toabout 10% by weight of the total composition.

Other agents such as thickeners, plasticizers, elastomers,thermoplastics, coloring agents, shelf-life extenders (for example, zincchloride), industrial microbiostats (for example, zinc omadine®)powder), surfactants or wetting agents, polymerization inhibitors,stabilizers, viscosity modifiers, adhesion promoters, and otherwell-known additives also may be incorporated where functionallydesirable. Moreover, spacer beads (such as 5 mil glass beads) also maybe included to control bond line thickness.

The present inventive compositions can be applied to any suitablesubstrate in accordance with the present inventive methods andprocesses. It is particularly useful to apply the present inventivecompositions to surfaces that are known to be difficult to bondtogether, such as flaky and smooth galvanized (i.e., zinc-coated orzinc-alloy coated) surfaces.

In that regard, it is well-known that, when attempting to bond togethergalvanized surfaces by means of conventional adhesive compositions,initial adhesion is often lost due to the exchange of the attachmentsite on the galvanized surface for water (due to the fact that zinccoordination to the adhesive composition is less preferred than water).Furthermore, exchange of the attachment site promotes rapid corrosion,which can be exacerbated by contaminants in the grain boundaries on thegalvanized surfaces. Moreover, it is well-known that the surfacemorphology of flaky galvanized surfaces renders them more difficult tobond together as opposed to smooth galvanized surfaces (because watermore easily replaces the coordination with zinc when the galvanizedsurface is flaky).

As illustrated in the examples set forth below, the present inventivecompositions, however, unexpectedly demonstrate superior bond strengthon both flaky and galvanized surfaces under various conditions,particularly under conditions of heat and humidity. Moreover, thepresent inventive compositions can be used in accordance with thepresent inventive processes for inhibiting corrosion on galvanizedsurfaces, thereby minimizing and,/or preventing corrosion that can occuron galvanized surfaces over prolonged periods of time.

Table I below shows various compositions which were made. Composition Ais a commercially available composition. Compositions B-G and I-Krepresent the inventive compositions made in accordance with the presentinvention. TABLE 1 Inventive Compositions B-G and I-K Prior Art A B C DE F G I J K Component Wt % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt.% Wt. % HYPALON 30 10.12 19.40 14.23 14.23 13.93 13.90 17.80 14.02 12.8612.90 (toughener) METHYL 51.51 44.77 53.48 52.74 51.40 51.27 41.53 48.7250.60 50.47 METHACRYLATE (MA) NAUGARD BHT 1.76 0.88 0.65 0.65 0.63 0.630.81 0.64 0.58 0.59 (antioxidant) SODIUM EDTA 0.04 0.18 0.13 0.13 0.130.13 0.16 0.13 0.12 0.12 SALT (chelator) HYDROQUINONE 0.09 0.09 0.060.06 0.06 0.06 0.08 0.06 0.06 0.06 BLENDEX 338 19.14 15.08 16.87 16.6516.24 16.20 13.99 15.65 15.90 15.97 (toughener) WAX 0.19 0.37 0.39 0.390.38 0.38 0.34 0.39 0.37 0.37 t-ButylPer- 0.82 0.88 0.65 0.65 0.63 0.630.81 0.64 0.58 0.59 Benzoate Accelerator¹ 1.69 1.69 1.33 1.29 1.25 1.251.69 1.67 1.66 1.69 MHORMER 9.68 10.41 7.63 7.63 7.47 7.46 9.55 7.526.90 6.92 BM-905 Surfactant — — — — — 0.13 — — — — 5 MIL GLASS — — — — —— — 0.20 0.20 0.20 BEADS Thixotropic — — — — — — — 0.33 0.33 0.33 agentThixotropic 0.86 — — — — — — — — — agent ZINC CHLORIDE 0.04 — — — — — —— — — TiO2 — — — — — — — 0.40 0.40 0.10 BLACK DISP'N — — — — — — — 0.080.15 — RV-262 Yellow Dye — — — — — — — — — 0.04 Catalyst² — — — — — — —— — 0.01 Blue Dye — — — — — — — — — 0.02 METHACRYLIC 1.41 3.53 2.59 2.592.53 2.53 3.24 2.55 2.34 2.34 ACID Phosphate 2.64 2.73 2.00 2.00 2.002.00 2.73 2.00 1.99 1.99 Ester³ Calcium — — — — — — 7.27 — 5.30 5.32Phospho- silicate⁴ BARIUM — — — — — — — 5.00 — — METABORATE⁵Benzothiazole — — — — 1.33 1.33 — — — — succinate⁶ Inhibitor⁷ — — — 1.00— 0.60 — — — — Bacterioside — — — — 2.00 3.50 — — — — Total 100 100 100100 100 100 100 100 100 100 Percentage Total Acid 4.05 6.25 4.59 4.594.53 4.53 5.96 4.55 4.33 4.34 (T-Mulz + MA)¹Pyridine derivative sold under tradename REILLCAT ASY-2.²Copper naphthenate in methyl methacrylate³T-Mulz 1228 sold by Hacros Organics, Kansas City, MO.⁴Corrosion inhibitor (Halox CW 491) sold by Halox Pigments, Hammond, IN.⁵Corrosion inhibitor available from Caschem, Inc., Bayonne, NJ.⁶Corrosion inhibitor IRGACOR 252 LD, sold by Vanticor.⁷8-Hydroxyquinoline.

EXAMPLE 1

This example demonstrates the superior ability of the present inventivecompositions to bond to flaky galvanized surfaces.

Compositions A, C, I, and J were prepared in accordance with Table 1.Composition A is a commercially available sold by Henkel Loctite (Hysol4500). Compositions C, I, and J are inventive compositions. As set forthin Table 1, Compositions A, C, I, and J all contained a phosphate estercomponent (i.e., T-Mulz 1228) in combination with methacrylic acid, withinventive Compositions C, I, and J containing at least 2 wt. % ofmethacrylic acid. Moreover, inventive Compositions I and J alsocontained a corrosion inhibitor.

Lap shear specimens were prepared for Composition A, which served as acomparative prior art composition, and for inventive Compositions C, I,and J using flaky, hot-dipped galvanized steel substrates. The specimenshad a ½ inch by 1 inch overlap and 0.000-0.005 inch bond line gap.

Tensile lap strengths (TLS) were measured under several conditions: atroom temperature; after humidity aging for 250 hours at 85° C. and 85%relative humidity; after humidity aging for 500 hours at 85° C. and 85%relative humidity; after humidity aging for 750 hours at 85° C. and 85%relative humidity; and after humidity aging at 85° C. and 85% relativehumidity for 1000 hours. Additionally, with respect to Compositions Iand J, tensile lap strength was measured after humidity aging at 120° F.and 100% relative humidity for 500 hours and after humidity aging at120° F. and 100% relative humidity for 1000 hours. The specinens werepulled at 0.5 inches/minute using an Instron testing machine inaccordance with American Standard Test Measurement (ASTM) D1002. Theresults of the aforementioned measurements are shown in Table 2. TABLE 2Tensile Lap Strength of Prior Art Composition A and InventiveCompositions C, I, and J Applied to Flaky Galvanized Steel Compo- Compo-Compo- sition C sition I sition J Prior Art Tensile Tensile TensileComposition A Lap Lap Lap Tensile Lap Strength Strength StrengthConditions Strength (psi) (psi) (psi) (psi) 0 hour @ 2406 2721 2532 279085° C./85% RH¹ (i.e., room temperature) 250 hours @ 617 877 1356 101885° C./85% RH 500 hours @ 0 136 1082 408 85° C./85% RH 750 hours @ 0 01183 111 85° C./85% RH 1000 hours @ 0 0 1002 0 85° C./85% RH 500 hours @— — 2409 2496 120° F./100% RH 1000 hours @ — — 2087 2773 120° F./100% RH¹Relative Humidity

As is apparent from Table 2 comparative Composition A exhibited initialtensile strength at room temperature but dramatically lost tensilestrength when subjected to conditions of heat and humidity.Specifically, Composition A lost approximately 74% of its tensilestrength after humidity aging at 250 hours and exhibited no tensilestrength after 500 hours.

As is further apparent from Table 2, Compositions C, I, and J allexhibited greater tensile strength than Composition A at roomtemperature (i.e., after humidity aging at 85% relative humidity and 85°C. for 0 hours), with Composition C exhibiting a tensile strength of2721 psi, Composition I exhibiting a tensile strength of 2532 psi, andComposition J exhibiting a tensile strength of 2790 psi. Moreover,Compositions C, I, and J all exhibited greater strength than CompositionA after humidity aging at 85% relative humidity and 85° C. for 250 hoursand after humidity aging at 85% relative humidity and 85° C. for 500hours.

Importantly, Compositions I and J also exhibited significant tensilestrength after humidity aging at 85% relative humidity and 85° C. for750 hours. and Composition I exhibited significant tensile strengthafter humidity aging at 85% relative humidity and 85° C. for 1000 hours.Additionally, Compositions I and J each exhibited significant tensilestrength after humidity aging at 120° F. and 100% relative humidity for500 hours and significant tensile strength after humidity aging at 120°F. and 100% relative humidity for 1000 hours.

EXAMPLE 2

This example demonstrates the superior ability of the present inventivecompositions to bond to smooth galvanized surfaces.

Inventive Compositions B, D, E, F, and G were prepared in accordancewith Table 1. As delineated in Table 1, Compositions B, D, E, F, and Gall contained a phosphate ester component.

Lap shear specimens were prepared for Compositions B, D, E, F, and Gusing smooth, hot-dipped galvanized steel substrates. The specimens had½ inch by 1 inch overlap and “zero” inch gap. Tensile lap strength wasmeasured again wider a variety of conditions: at room temperature (ie.,after humidity aging at 85° C. and 85% relative humidity for 0 hours);after humidity aging at 85° C. and 85% relative humidity for 250 hours;after humidity aging at 85° C. and 85% relative humidity for 750 hours;and after humidity aging at 85° C. and 85% relative humidity for 1000hours. Additionally, tensile lap strength was measured after humidityaging at 120° F. and 100% relative humidity for 500 hours and afterhumidity aging at 120° F. and 100% relative humidity for 1000 hours. Thespecimens were pulled at 0.5 inches/minute in accordance with AmericanStandard Test Measurement (ASTM) D1002. The results of theaforementioned measurements are shown in Table 3. TABLE 3 Tensile LapStrength of Inventive Compositions B, D, E, F, and G Applied to SmoothGalvanized Steel at “Zero” Gap Compo- Compo- Compo- Compo- Compo- sitionB sition D sition E sition F sition G 0 hours @ 2528 2226 2586 2017 288285° C./85% RH¹ (i.e., room temperature) 250 hours @ 2942 2528 2793 24843242 85° C./85% RH 500 hours @ 2099 2466 2724 2220 3032 85° C./85% RH750 hours @ 2470 2650 2614 1702 2578 85° C./85% RH 1000 hours @ 14142369 2161 2229 2021 85° C./85% RH 500 hours @ 2404 2435 2258 2095 2414120° F./100% RH 1000 hours @ 2430 2613 2334 2399 2159 120° F./100% RH¹Relative humidity

As is apparent from Table 3, all of the tested compositions exhibited atensile strength of at least 2000 psi at room temperature, withComposition G exhibiting a tensile strength of 2882 psi. Moreover, allof the tested compositions exhibited significant tensile strength whensubjected to conditions of heat and humidity, Specifically, all of thetested compositions exhibited a tensile strength of at least 2400 psiafter humidity aging at 85° C. and 85% relative humidity for 250 hours,with Composition G exhibiting a tensile strength of 3242 psi.Furthermore, all of the tested compositions exhibited a tensile strengthof at least 2000 psi after humidity aging at 85° C. and 85% relativehumidity for 500 hours, with Composition G exhibiting a tensile strengthof 3032 psi. Even after humidity aging at 85° C. and 85% relativehumidity for 1000 hours, all of the tested compositions exhibitedtensile strength, with four of the five tested compositions (i.e.,Compositions D-G) exhibiting a tensile strength of at least 2000 psi.Moreover, all of the compositions exhibited significant tensile strengthafter humidity aging at 120° F. and 100% relative humidity for 1000hours, with Composition D exhibiting a tensile strength of at least 2613psi.

The examples set forth above serve to illustrate the present invention,but in no way are intended to limit the spirit and scope thereof, whichis defined by the following claims.

1. A curable composition for bonding galvanized surfaces comprising: (a)a first part comprising: (i) at least one curable (meth)acrylatecomponent; (ii) a free-radical initiator component: and (iii) aphosphate ester component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 1000 psi whenmeasured after humidity aging at 85% relative humidity and a temperatureof 85° C. for a period of time of 250 hours; and (b) a second partcomprising one or more of an accelerator component, a carrier component,and a free radical initiator component, wherein at Least one of thefirst part or the second part further comprises a corrosion inhibitor.2. The composition of claim 1, wherein the phosphate ester component ispresent in an amount sufficient to achieve at least a 20% increase intensile strength on galvanized surfaces as compared to the compositionin the absence of this component.
 3. The composition of claim 1, whereinthe second part comprises a corrosion inhibitor.
 4. The composition ofclaim 1, wherein the phosphate ester component includes a (meth)acrylatefunctional group on the same molecule.
 5. The composition of claim 1,wherein the phosphate ester component is represented by the formula:

wherein R¹ is H or CH₃, and R is H.
 6. The composition of claim 1,further comprising a toughening component.
 7. The composition of claim1, wherein the corrosion inhibitor includes a member selected from thegroup consisting of metal phospho-silicates, alkali metalphospho-silicates, and combinations thereof
 8. The composition of claim7, wherein the corrosion inhibitor is selected from the group consistingof calcium phospho-silicate, zinc phospho-silicate, barium metal borate,and combinations thereof.
 9. A method for using the composition of claim1 to bond together two substrates, comprising the steps of: (a) applyingthe composition to a first substrate surface; (b) mating the surface ofa second substrate in abutting relationship with the composition-appliedfirst substrate surface to form an assembly; and (c) maintaining theabutting relationship for a time sufficient to allow the composition tocure, wherein at least one of the abutting substrate surfaces isgalvanized.
 10. The method of claim 9, further comprising the step ofapplying the composition to both surfaces prior to placing them inabutting relationship.
 11. A process for inhibiting corrosion on agalvanized surface comprising the steps of: 1) applying to a galvanizedsubstrate surface the composition of claim 1, and 2) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.
 12. A composition comprising the reactionproduct of: (a) a first part comprising: (i) at least one curable(meth)acrylate component; (ii) a free-radical initiator component; and(iii) a phosphate ester component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 1000 psi whenmeasured after humidity aging at 85% relative humidity and a temperatureof 85° C. for a period of time of 250 hours; and (b) a second partcomprising one or more of an accelerator, a carrier component, a freeradical initiator component and combinations thereof, wherein at leastthe first part or the second part also comprises a corrosion inhibitor.13. An article of manufacture comprising at least two substrate surfacesbonded together with the composition of claim 1, wherein at least one ofthe substrate surfaces is galvanized.
 14. A curable composition forbonding galvanized surfaces comprising: (a) a first part comprising: (i)at least one curable (meth)acrylate component; (ii) a free-radicalinitiator component; (iii) a phosphate ester component; and (iv) anorganic acid component in an amount sufficient to achieve a tensilestrength on a galvanized surface of at least about 2500 psi at roomtemperature; and (b) a second part comprising one or more of anaccelerator component, a carrier component, and a free radical initiatorcomponent.
 15. A method for using the composition of claim 14 to bondtogether two substrates, comprising the steps of: (a) applying thecomposition to a first substrate surface, (b) mating the surface of asecond substrate in abutting relationship with the composition-appliedfirst substrate surface to form an assembly; and (c) maintaining theabutting relationship for a time sufficient to allow the composition tocure, wherein at least one of the abutting surfaces is galvanized.
 16. Aprocess for inhibiting corrosion on a galvanized surface comprising thesteps of: 1) applying to a galvanized substrate surface the compositionof claim 14, and 2) subjecting the composition-applied substrate surfaceto conditions sufficient to allow the composition to cure.
 17. Acomposition comprising the reaction product of: (a) a first partcomprising: (i) at least one curable (meth)acrylate component; (ii) afree-radical initiator component; (iii) a phosphate ester component; and(iv) an organic acid component in an amount sufficient to achieve atensile strength on a galvanized surface of at least about 2500 psi atroom temperature; and (b) a second part comprising one or more of anaccelerator, a carrier component, and a free radical initiatorcomponent.
 18. An article of manufacture comprising at least twosubstrate surfaces bonded together with the composition of claim 14,wherein at least one of the substrate surfaces is galvanized.
 19. Thecomposition of claim 14, wherein at least the first part or the secondpart also comprises a corrosion inhibitor.
 20. The composition of claim19, wherein the corrosion inhibitor is present in an amount sufficientto achieve a tensile strength on a galvanized surface of at least about400 psi when measured after humidity aging at 85% relative humidity anda temperature of 85° C. for a period of time of 500 hours.
 21. Thecomposition of claim 1, wherein the corrosion inhibitor is present in anamount sufficient to achieve a tensile strength on a galvanized surfaceof at least about 400 psi when measured after humidity aging at 85%relative humidity and a temperature of 85° C. for a period of time of500 hours
 22. A curable composition for bonding galvanized surfacescomprising: (a) a first part comprising: (i) at least one curable(meth)acrylate component; (ii) a free-radical initiator component; (iii)a phosphate ester component; and (iv) an organic acid component in anamount sufficient to achieve a tensile strength on a galvanized surfaceof at least about 800 psi when measured after humidity aging at 85%relative humidity and 85° C. for 250 hours; and (b) a second partcomprising one or more of an accelerator component, a carrier component,and a free radical initiator component.
 23. A method for using thecomposition of claim 22 to bond together two substrates, comprising thesteps of: (a) applying the composition to a first substrate surface; (b)mating the surface of a second substrate in abutting relationship withthe composition-applied first substrate surface to form an assembly; and(c) maintaining the abutting relationship for a time sufficient to allowthe composition to cure, wherein at least one of the abutting surfacesis galvanized.
 24. A process for inhibiting corrosion on a galvanizedsurface comprising the steps of: 1) applying, to a galvanized substratesurface the composition of claim 22, and 2) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.
 25. A composition comprising the reactionproduct of: (a) a first part comprising: (i) at least one curable(meth)acrylate component; (ii) a free radical initiator component; (iii)a phosphate ester component, and (iv) an organic acid component in anamount sufficient to achieve a tensile strength on a galvanized surfaceof at least about 800 psi when measured after humidity aging at 85%relative humidity and a temperature of 85° C. for a period of time of250 hours; and (b) a second part comprising one or more of anaccelerator component, a carrier component, and a free radical initiatorcomponent.
 26. A process for inhibiting corrosion on a galvanizedsurface comprising the steps of: 1) applying to a galvanized substratesurface the composition of claim 22, and 2) subjecting thecomposition-applied substrate surface to conditions sufficient to allowthe composition to cure.
 27. A composition comprising the reactionproduct of: (a) a first part comprising: (i) at least one curable(meth)acrylate component; (ii) an accelerator; (iii) a phosphate estercomponent; and (iv) an organic acid component in an amount sufficient toachieve a tensile strength on a galvanized surface of at least about 800psi when measured after humidity aging at 85% relative humidity and atemperature of 85° C. for a period of time of 250 hours; and (b) asecond part comprising: (i) a carrier component; and (ii) a free radicalinitiator component.
 28. An article of manufacture comprising at leasttwo substrate surfaces bonded together with the composition of claim 22,wherein at least one of the substrate surfaces is galvanized.